Analytical tools applied to the evaluation of the influence of different marine environments on the conservation state of building materials

362 p.Marine aerosol is a chemical complex system formed by inorganic salts and organic matter, together with airborne particulate matter from the surrounding environment. The primary particles transported in the marine aerosol (PMA) can experiment different chemical reactions in the atmosphere, promoting the so-called Secondary Marine Aerosol (SMA) particles. These kinds of particles, together with the natural crustal or mineral particles and the metallic airborne particulate matter emitted by anthropogenic sources (road traffic, industry, etc.) can be deposited on building materials from a specific construction following dry deposition processes. Apart from that, the acid aerosols (e.g. CO2, SO2, NOX, etc.) present in modern urban-industrial environments, coming also from anthropogenic sources, could be deposited in the buildings following dry or a wet deposition mechanisms. The interactions of these natural and anthropogenic stressors with building materials can promote different kind of pathologies.In this PhD work, the negative influence of different marine environments (direct or diffuse influence), with or without the influence of an urban-industrial area (direct or diffuse), on the conservation state of two historical constructions and some newly built houses from the Basque Country (north of Spain) was evaluated. These constructions include a wide variety of building materials (sandstones, limestones, artificial stones, bricks, plasters, cementitious materials, etc.). The analytical methodology applied for this purpose involved, in some case studies, the use of non-invasive portable/hand-held spectroscopic technique (ED-XRF and Raman spectroscopy) able to perform an in situ screening in order to extract preliminary results. After that, non-invasive spectroscopic techniques (micro-Raman spectroscopy, FT-IR, XRD, -ED-XRF, SEM-EDS), together with destructive techniques (ICP-MS and ion chromatographic), thermodynamic modellings and chemometric tools was also applied to extract the final conclusions about the pathologies identified on the constructions under study in relation with the specific marine environment where they are located.Thanks to the use of these analytical tools, it was possible to characterize different deterioration processes caused mainly by the influence of marine aerosol (wet and dry deposition), infiltration waters, birds droppings, salts migrations, atmospheric acid gases impact, biological colonizations, etc. Moreover, the characterization of the PMA particles and SMA particles was conducted, thanks to the development of a home-made passive sampler in the last case. Additionally, the deposition of this kind of particles on sandstone, following dry deposition processes, was also confirmed

Analytical tools applied to the evaluation of the influence of different marine environments on the conservation state of building materials

362 p.Marine aerosol is a chemical complex system formed by inorganic salts and organic matter, together with airborne particulate matter from the surrounding environment. The primary particles transported in the marine aerosol (PMA) can experiment different chemical reactions in the atmosphere, promoting the so-called Secondary Marine Aerosol (SMA) particles. These kinds of particles, together with the natural crustal or mineral particles and the metallic airborne particulate matter emitted by anthropogenic sources (road traffic, industry, etc.) can be deposited on building materials from a specific construction following dry deposition processes. Apart from that, the acid aerosols (e.g. CO2, SO2, NOX, etc.) present in modern urban-industrial environments, coming also from anthropogenic sources, could be deposited in the buildings following dry or a wet deposition mechanisms. The interactions of these natural and anthropogenic stressors with building materials can promote different kind of pathologies.In this PhD work, the negative influence of different marine environments (direct or diffuse influence), with or without the influence of an urban-industrial area (direct or diffuse), on the conservation state of two historical constructions and some newly built houses from the Basque Country (north of Spain) was evaluated. These constructions include a wide variety of building materials (sandstones, limestones, artificial stones, bricks, plasters, cementitious materials, etc.). The analytical methodology applied for this purpose involved, in some case studies, the use of non-invasive portable/hand-held spectroscopic technique (ED-XRF and Raman spectroscopy) able to perform an in situ screening in order to extract preliminary results. After that, non-invasive spectroscopic techniques (micro-Raman spectroscopy, FT-IR, XRD, -ED-XRF, SEM-EDS), together with destructive techniques (ICP-MS and ion chromatographic), thermodynamic modellings and chemometric tools was also applied to extract the final conclusions about the pathologies identified on the constructions under study in relation with the specific marine environment where they are located.Thanks to the use of these analytical tools, it was possible to characterize different deterioration processes caused mainly by the influence of marine aerosol (wet and dry deposition), infiltration waters, birds droppings, salts migrations, atmospheric acid gases impact, biological colonizations, etc. Moreover, the characterization of the PMA particles and SMA particles was conducted, thanks to the development of a home-made passive sampler in the last case. Additionally, the deposition of this kind of particles on sandstone, following dry deposition processes, was also confirmed

Use of portable devices and confocal Raman spectrometers at different wavelength to obtain the spectral information of the main organic components in tomatoes (Solanum Lycopersicum) fruits

Tomato (Solanum lycopersicum) fruit samples, in two ripening stages, ripe (red) and unripe (green), collected from a cultivar in the North of Spain (Barrika, Basque Country), were analyzed directly, without any sample pretreatment, with two different Raman instruments (portable spectrometer coupled to a micro-videocamera and a confocal Raman microscope), using two different laser excitation wavelengths (514 and 785 nm, only for the confocal microscope). The combined use of these laser excitation wavelengths allows obtaining, in a short period of time, the maximum spectral information about the main organic compounds present in this fruit. The major identified components of unripe tomatoes were cutin and cuticular waxes. On the other hand, the main components on ripe tomatoes were carotenes, polyphenoles and polysaccharides. Among the carotenes, it was possible to distinguish the presence of lycopene from b-carotene with the help of both excitation wavelengths, but specially using the 514 nm one, which revealed specific overtones and combination tones of this type of carotene.This work has been financially supported by Research Project S-PE11-UN128 of the Basque Country government. Technical and support provided by SGIker (UPV/EHU, MICINN, GV/EJ, ESF) is gratefully acknowledged

Nature and origin of white efflorescence on bricks, artificial stones, and joint mortars of modern houses evaluated by portable Raman spectroscopy and laboratory analyses

Bricks and mortar currently constitute one of the most important building materials used in the construction of most modern facades. The deterioration of these materials is caused primarily by the impact of numerous external stressors, while poor manufacturing quality, particularly of mortars, can also contribute to this process. In this work, the non-invasive Raman spectroscopy technique was used to identify the recently formed deterioration compounds (primarily sulfates and nitrates) in bricks, artificial stones, and joint mortars from detached houses in the Bilbao metropolitan area (Basque Country, North of Spain), as well as to investigate the deterioration processes taking place in these materials. Additionally, to confirm and in some cases complement the results obtained with Raman spectroscopy, SEM-EDS and XRD measurements were also carried out.This work was financially supported by DEMBUMIES (ref.BIA2011-28148) and funded by the Spanish Ministry of Economy and Competitiveness (MINECO). H. Morillas is grateful to the University of the Basque Country (UPV-EHU) and particularly to the UFI 11-26 Global Change and Heritage, who funded his pre-doctoral fellowship. Technical support provided by the Raman-LASPEA and General X-ray Service: Rocks and Minerals laboratories of SGIker (UPV/EHU, MICINN, GV/EJ, ERDF and ESF) is also gratefully acknowledged

Portable and Raman imaging usefulness to detect decaying on mortars from Punta Begoña Galleries (Getxo, North of Spain)

Punta Begoña Galleries were built in 1918 in Getxo (Basque Country, North of Spain) but were abandoned in 1960. Nowadays, their conservation state is very poor. In this work, portable Raman spectroscopy was applied to evaluate the original composition and possible deterioration products of the mortars used in the inner walls and those covering the concrete of the ceilings allowing us to select the most appropriate sampling points. In the laboratory, Raman microscopy and Raman imaging, assisted with scanning electron microscopy equipped with an energy dispersive spectrometer (SEM‐EDS), X‐ray diffraction and energy dispersive X‐ray fluorescence (ED‐XRF) imaging, allowed to identify the key compounds to understand the deterioration processes taking place in the mortars of the galleries. The main components of the mortars from the walls were calcite and gypsum. In some cases, alite (Ca3SiO5) and belite (Ca2SiO4) were identified; these components are characteristic of Portland cement clinker. The main components of the mortar covering the concrete were calcite, quartz, aragonite and gypsum. The aragonite identification confirmed the use of beach sand as the aggregate in the mortar. The concrete from the ceiling of the lower gallery is covered with three different mortar layers; the outermost layer is covered with a black crust. In the three mortars, the main components are similar to those used in the mortar covering the concrete from the upper gallery. Thanks to Raman, ED‐XRF and SEM‐EDS imaging, it was possible to map the distribution of the main components through the three mortar layers and also to identify the presence of dolomite {[CaMg(CO3)2]}, which was not possible to detect following single‐point micro‐Raman analyses.This work has been funded by the Ministry of Economy and Competitiveness and the European Regional Development Fund (ERDF) through the project DISILICA‐1930 (ref. BIA2014‐59124‐P) and by the cooperation agreement between the University of the Basque Country (UPV/EHU) and the City Council of Getxo (OTRI2014‐0639). C. García‐Florentino is grateful to the University of the Basque Country (UPV/EHU), which funded her predoctoral fellowship. Technical support provided by Raman‐LASPEA Laboratory and General X‐ray Service of the SGIKer (UPV/EHU, Ministry of Economy and Competitiveness of Spain, Basque Government, ERDF and European Social Fund) is also gratefully acknowledged

PM10 spatial distribution and metals speciation study in the Bilbao metropolitan area during the 2017–2018 period

Speciation of respirable particles is becoming increasingly important from an epidemiological and analytical point of view to determine the potential effects of air pollution on human health. For this reason, current laws and analytical sampling methods focus on particle size, as it turns out to be the main factor for the greater or lesser penetration into the airways. In this sense, particles of less than 10 μm in diameter (<10 μm), referred to as PM10, are the particles that have a higher capacity for access to the respiratory tract and, therefore, more significant effect on them. In this sense, one of the most important factors that have a key role in the PM10 atmospheric pollution effect is the dispersion effect with the direct influence of natural effects such as wind, rain, topography apart from others. In this work, PM10 data extracted from the Basque Government environmental stations (19 sampling points) in the Biscay province (Basque Country, north of Spain) were combined with the results obtained from the use of self-made passive samplers (SMPS) in the same sampling points areas and subsequently, the sample analysis with a non-invasive elemental technique (Scanning Electron Microscope coupled to Energy Dispersive X-ray Spectrometry) was carried out. Thanks to this methodology, it was possible to determine a wide variety of metals in PM10 such as Al, Fe, Cr, Ni, Pb, Zn, Ti, etc. Most of them present as oxides and others as part of natural aggregations such as quartz, aluminosilicates, phosphates etc

The influence of marine environment on the conservation state of Built Heritage: an overview study

Marine aerosol is a chemical complex system formed by inorganic salts and organic matter, together with airborne particulate matter from the surrounding environment. The primary particles transported in the marine aerosol can experiment different chemical reactions in the atmosphere, promoting the so-called Secondary Marine Aerosol particles. These kinds of particles (nitrates, sulfates, chlorides etc.), together with the natural crustal or mineral particles and the metallic airborne particulate matter emitted by anthropogenic sources (road traffic, industry, etc.) form clusters which then can be deposited on building materials from a specific construction following dry deposition processes. Apart from that, the acid aerosols (e.g. CO2, SO2, NOX, etc.) present in urban-industrial environments, coming also from anthropogenic sources, can be deposited in the buildings following dry or a wet deposition mechanisms. The interactions of these natural and anthropogenic stressors with building materials can promote different kind of pathologies. In this overview, the negative influence of different marine environments (direct or diffuse influence), with or without the influence of an urban-industrial area (direct or diffuse), on the conservation state of historical constructions including a wide variety of building materials (sandstones, limestones, artificial stones, bricks, plasters, cementitious materials, etc.) is presented

Evaluation of black crust formation and soiling process on historical buildings from the Bilbao metropolitan area (north of Spain) using SEM-EDS and Raman microscopy

In the present work, several building materials suffering from black crusts and soiled surfaces were evaluated by scanning electron microscopy energy dispersive X-ray spectrometry (SEM-EDS) and micro-Raman spectroscopy. The goal was to examine the elemental and molecular composition, the distribution on the samples, and the morphology of endogenous and exogenous compounds on those black crusts and soiled surfaces. The black crusts were deposited over different building materials such as limestone, sandstone, and brick that constitute a small construction called "malacate" as well as over a limestone substrate of a cemetery gate. Both constructions are dated back to the beginning of the twentieth century. The samples of soiling were taken from the façade of a building constructed in the 1980s. The analytical evaluation allowed in a first stage the determination of the composition and the observation of the morphology of soiling and black crusts. In addition, the evaluation of the compositions of the soiling and black crusts of different grade and formation allowed the assessment of the main weathering phenomena that the buildings have suffered, which were found to be sulfate impact, marine aerosol impact, depositions of metallic particles, crustal particulate matter depositions, carbonaceous particles, biodeterioration, and vandalism.This work has been funded by the Spanish Ministry of Economy and Competitiveness (MINECO) through the project DISILICA-1930 (ref. BIA2014-59124-P) and the Regional Development Fund (FEDER). E. Calparsoro is grateful also to the Spanish Ministry of Economy and Competitiveness (MINECO) who funded his pre-doctoral fellowship (ref. BES-2014-068940)

Characterization of restoration lime mortars and decay by-products in the Meditation area of Machu Picchu archaeological site

Machu Picchu citadel is the main archaeological Inca sanctuary widely known around the world, and a World Heritage Site of high cultural and natural value. For its construction a whitish granitic rock, extracted from the “Vilcapampa or Vilcabamba” batholith formation was used. During time, some of the granitic rocks from the natural stonewalls of the Meditation area of the Archaeological Park were restored. For the restoration works done in the 50s' a specific lime mortar called Clarobesa was used. After the inclusion of this joining mortar, many efflorescences are nowadays visible in the mortar itself and on the surface of the edges of the annexed rocks. To evaluate the possible impact of these salts crystallizations in the conservation state of these natural stonewalls, a multi-analytical methodology was designed and applied. With a combination of non-invasive and destructive techniques such as X-ray Diffraction, Raman microscopy, Scanning Electron Microscope coupled to an Energy Dispersive X-ray Spectrometer and ion chromatography, the mineralogical composition and the nature/concentration of the soluble salts present in the Clarobesa mortar was determined. The experimental results suggest that Clarobesa mortar is a hydraulic lime mortar. The study of salts crystallizations by Raman microscopy allowed identifying the presence of calcium sulfates with different hydration waters and also nitrates. In some samples, the concentration of sulfates was high, reaching values up to 10% w/w. Although the concentration of nitrates is not extremely high, a clear contribution of ammonium nitrates coming from the decomposition of the nearby vegetation was assessed. Since the Clarobesa mortar can be considered an important input of ions that can migrate to the joined granitic rocks, in the future, it will be recommendable to monitor possible changes in the conservation state of the joined rocks

Evaluating sulfates and nitrates as enemies of the recent constructions: Spectroscopic and thermodynamical study

Salt crystallization is one of the major problems currently faced by the field of architecture and construction. Its effects are devastating to the extent that they may even lead to loss of material. Although many innovative and resistant materials have been developed in the last years, in most of the constructions, salt crystallization is a persistent problem. Salts crystallizations are formed by the dissolution and subsequent precipitation of the soluble salts present in the material itself or due to the formation of new ones because of the reaction between original components of the building materials with salts coming from infiltration waters or with acid aerosols present in the atmosphere. Among others, some of the most common salts that can crystallize in the building materials are nitrates and sulfates. Both of them are soluble compounds, which can mobilize throughout the material easily, reprecipitate, and generate volume changes responsible for fissures, fractures, and even the loss of building material. In this work, a specific study of salts crystallizations in a recent construction erected in 2013 in Amorebieta (Basque Country, North of Spain) using a different kind of materials has been studied. The materials affected by salts are joint mortars, which in a first step were characterized by X‐ray diffraction and Raman microscopy to determine the mineralogical composition. In a second step, a soluble salts tests by ion chromatography was applied to approach quantitatively the impact of the salts. Finally, in a third step, the reactions that give rise to the decay products (thenardite, nitrocalcite, and/or epsomite mainly) were proposed and confirmed through a thermodynamic modellin